Fluorine-containing organosilicon compounds

ABSTRACT

Silanes and siloxanes having at least one group of the general formula CnF2n-1RaCmH2mSiR&#39;&#39;bXcO(4-b-c)/2 where R is a divalent group, R&#39;&#39; is a monovalent hydrocarbon group, X is a hydrolysable group, n is 8, 10 or 12, a is 0 or 1, m is 2, 3 or 4, b is Q, 1 or 2, c is 0, 1, 2 or 3 and b + c is not greater than 3, and uses thereof e.g., in surface treatment of glass fibres.

United States Patent Atherton Jan. 7, 1975 FLUORINE-CONTAINING 3,012,00612/1961 ORGANOSILICON COMPOUNDS [75] Inventor: John Heathcote Atherton,3:560:54z 2 1971 Manchester, England 3,681,266 8/1972 [73] Assignee:Imperial Chemical Industries 368l4l8 8/1972 Limited, London, EnglandPrimary ExaminerDaniel E. Wyman [22] Flled' Mar. 1973 AssistantExaminerPaul F. Shaver [21] Appl. N0.: 339,764 Attorney, Agent, orFirmCushman, Darby &

Cushman [30] Foreign Application Priority Data May 22, 1972 GreatBritain 23888/72 [57] ABSTRACT [52] US. Cl .260/448.2 N, 117/124 F,

117/126 65 117/126 GN 260/37, S1lanes and s1loxanes havmg at least onegroup of the 260/448 2 E 260/4482 B 260/448.8 R general formula C,,F,,,,R,,C,,,H,,,,S1R ,X,.O where [51] int. CLW'M C0'7b 7708, C07b 7/l0CO-Ib 7/18 R is a d1valent group, R is a monovalent hydrocarbon [58]Field of Search ..260/448.8 R, 448.2 N, group X is a hydrolysable groupis 260/4482E 4482B O0r1,mis2,3or4,bisQ,1or2,cis(),l,2or3 and b c is notgreater than 3, and uses thereof e.g., [56] References Cited in surfacetreatment of glass fibres.

UNITED STATES PATENTS 10/1961 Johannson 260/448.8 R X 8 Claims, N0Drawings FLUORINE-CONTAINING ORGANOSILICON COMPOUNDS This inventionrelates to fluorine-containing organosilicon compounds and moreparticularly to silanes and siloxanes having one or more unsaturatedfluorocarbon substituted groups therein.

A number of silanes or siloxanes are known or have be proposed whichcontain fluorocarbon groups. In all of these the fluorocarbon group hasbeen a saturated group. Because of their nature these materials sufferfrom various disadvantages, for example, such a high cost.

According to the present invention a new class of silanes and siloxanescomprising at least one group of the general formula:

where R is a divalent group, R is a monovalent hydrocarbon group, X is ahydrolysable group, n is 8, 10 or l2,aisor l,mis2,3 or4,bis0, 1or2,cis0, 1, 2 or 3 and b c is not greater than 3.

The siloxanes of our invention may contain in addition to the abovespecified groups, units of one or more of the general formulae:

Z SiO z,sio, ZSiO sio,, ZHSiO and Hz,sio,,

where Z is a monovalent hydrocarbon group of the kind well known insiloxanyl units. It is in fact frequently preferred that Z be a methylgroup.

The group R may be oxygen, an alkylene group having not more than 8carbon atoms, a polyoxyalkylenediol residue or a phenyleneoxy orsubstituted phenyleneoxy group. Monovalent substituents which may bepresent in the phenyleneoxy group include alkyl and alkoxy groups andhalogen atoms. Divalent substituents which may be present alone or inaddition include sulphonamido and carboxyl groups to link thephenyleneoxy group to the group C,,,H

The groups R may be alkyl, aryl, alkaryl, aralkyl, or cycloalkyl groups,for example, such as methyl, ethyl, propyl or phenyl groups. It is ingeneral preferred that the groups R be methyl groups.

The group X may be, for example, a halogen atom, an alkoxy group, asubstituted alkoxy group or a polyoxyalkylene group. Suitable groupsinclude, for example, fluorine, chlorine, bromine, methoxy, ethoxy,propoxy, butoxy, methoxyethoxy, ethoxyethoxy, phenoxy and2-(N,N-dimethylamino)ethoxy groups. It is normally preferred that thegroups X be chlorine, methoxy or ethoxy groups.

In one method of preparing the compounds of our invention, where R is aphenyleneoxy group or substituted phenyleneoxy group, an unsaturatedtetrafluoroethylene oligomer of general formula:

where n is 8, 10 or 12 may be first reacted with an allylphenol orsubstituted allylphenol after which the compound so prepared is reactedwith a silane or siloxane containing at least one silicon-bondedhydrogen atom. The reaction with the allylphenol or substitutedallylphenol may be carried out by stirring the reactants together inpresence of a solvent such as dimethylformamide and an acid acceptorsuch as triethylamine. The product of this reaction is then reacted witha compound containing silicon-bonded hydrogen in presence of a suitablecatalyst. These products may also be prepared by first preparing acompound of the oligomer and a sulphonyl chloride substituted phenol,e.g., as described in UK. Pat. application No. 8295/7l, and reactingthis with a suitable y-aminoalkyl silane or siloxane, e.g.,y-aminopropyltriethoxysilane or alternatively by reacting thephenol/oligomer compound with an amino-olefin such as3-aminopropyl-l-ene and then reacting the product with a silane orsiloxane containing at least one silicon-bonded hydrogen atom.

In another method of preparing the compounds of our invention, where ais 0, a tetrafluoroethylene oligomer may be reacted with an alkenylmagnesium bromide and the reaction product thereafter reacted with asilane or siloxane containing at least one siliconbonded hydrogen atom.The reaction may be carried out by simultaneously adding the alkenylbromide and a tetrafluoroethylene oligomer to a stirred suspenio n ofmagnesium in diethyl ether and thereafter reacting the product soobtained with the silicon compound.

The reaction of the allyl fluoro compound with the silane or siloxanecontaining at least one siliconbonded hydrogen atom may be carried outin known manner and in the presence of a catalyst of the kind known tobe suitable for such reactions. Suitable catalysts include, for example,chloroplatinic acid, cyclohexene platinum- (ll)-chloride andbis(diethylsulphide) platinum-(ll)-chloride.

Suitable silanes for use in this reaction include, for example,trichlorosilane, methyl-dichlorosilane, dimethylchlorosilane,trimethoxysilane, triethoxysilane, methyldiethoxysilane anddimethylmethoxysilane.

The siloxanes of our invention can be made either directly or byhydrolysis of a silane of our invention alone or in presence of one ormore other hydrolysable silanes. They may also be produced byequilibration.

The products of our invention have a wide variety of uses. For example,they may be used to render the surface of glass hydrophobic andoleophobic, and are thus useful for the treatment of glazing inagricultural buildings, e.g., greenhouses, and in the treatment of glassfibres for use as filters for liquids and gases. They are also of valueas antifoam agents especially in nonaqueous systems and as releaseagents.

Fluorocarbon derivatives containing silane or siloxane groups may beused for the treatment of fillers, e.g., glass fillers in themanufacture of filled granular grades of fluorocarbon polymers.Preferably the filler is treated with a solution of the derivative in anorganic solvent to coat the filler with the derivative and make ithydrophobic prior to agglomerating it with the fluorocarbon polymer froman aqueous medium.

Fluorocarbon derivatives containing a C,,F group where n=8, 10 or 12linked to a group of formula:

e.g., compounds comprising at least one group of formula:

where R, R, X, n, a, m, b and c are as defined above may be used.Particularly useful derivatives are compounds of the formulae:

and

c.orwocsmz-Nmcnzia u zmia The formation of relatively small sizeagglomerates of a fluorocarbon polymer and filler is important inmoulding technology as it enables free flowing filled particles to beformed from poorly flowing polymer. The particles can be more readilyhandled than unagglomerated polymer and filler, e.g., in automatic mouldmachinery.

By making the filler particles hydrophobic with a surfactant which willwithstand the washing conditions experienced in agglomeration from anaqueous medium, as further described below, the successful agglomerationof polymer and filler is facilitated. In practical terms this means thata substantial proportion of the filler charged to the wash vessel willunder suitable conditions be agglomerated with the fluorocarbon polymer.Thus waste of filler will be minimized and the composition of theagglomerated product will be predictable from the relative amounts ofpolymer and filler charged. It has thus proved a valuable discovery thatfluorocarbon derivatives as described above can be used to treat fillerssuccessfully in this agglomeration method.

Fluorocarbon polymers in granular form are made by methods well known inthe art for example by polymerizing monomer in an aqueous medium in theabsence of a stabilizing amount of emulsifying agent. The polymerrecovered is usually comminuted, e.g., by milling, before a filler isincorporated into it. The fluorocarbon polymers include granular gradesof polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylenewith up to 15 percent by weight of other monomers such as ethylene,vinyl chloride and hexafluoropropene.

The fillers that may be treated prior to incorporation into thefluorocarbon polymer in addition to glass include metallic fillers suchas aluminium, bronze, copper, nickel and iron and mineral fillers suchas asbestos, mica, silica and talc. In an agglomeration from an aqueousmedium there is generally no need to treat fillers which are alreadyhydrophobic, e.g., graphite, to assist in their agglomeration with thepolymer.

In carrying out an agglomeration from an aqueous medium the granularpolymer and filler, both in fine particle form, the filler having beentreated with the fluorocarbon derivative, may be charged to a washingvessel in which they are agitated with water by suitable stirring meansuntil agglomerates of a suitable size and containing both the polymerand filler are formed. The agglomerates are subsequently recovered fromthe vessel and dried. A suitable agitation period is from two to fourhours at 60 to 90C. Milled granular PTFE of 20-25 pm mean particle sizeis a suitable form of polymer to use, e.g., with finely divided glassfibres.

Our invention is further illustrated by the following examples in whichall parts and percentages are by weight.

EXAMPLE 1 1,500 parts of tetrafluoroethylen'e pentamer, 1,300 parts ofdimethylformamide, 482 parts of o-allylphenol and 380 parts oftriethylamine were stirred together for 28 hours at 25C. The lower layerwas then allowed to settle, separated, washed successfully with 1,500parts of 5 percent aqueous sulphuric acid and 1,500 parts of water, andthen dried azeotropically by refluxing with toluene under a Dean-Starkseparator. In addition to water, 262 parts of tetrafluoroethylenepentamer were removed via the Dean-Stark separator. Toluene wasdistilled off and the residue fractionated in vacuo. 1,168 parts of thecompound EXAMPLE 2 123 parts of compound A and 0.046 part of bis(-diethylsulphide) platinum(ll)chloride were heated to C and 50 parts ofmethyl-dichlorosilane added dropwise over a period of 5 minutes. Themixture was refluxed for 1% hours and then distilled in vacuo. Therewere thus obtained 92.5 parts of MeCIZSi- (CH2)3O-C H4OC10Hm, mm. Found:C, 33.0, 32.9; H, 1.85, 1.85; Cl, 9.85, 9.70%. Calc. for C H Cl F OSi C,32.9; H, 1.8; CI, 9.7%.

EXAMPLE 3 A mixture of 281 parts of compound A, 300 parts of toluene and0.125 part of bis(diethylsulphide) platinum(II) chloride was heated toreflux. 66.6 parts of trimethoxysilane were added dropwise to therefluxing solution, which was maintained at reflux for 6% hours afterthe addition was completed. Distillation in vacuo yielded 232 parts of(MeO) Si(CH oC H OC F, b.p. 124l25/0.05 mm.

Found: C, 36.2, 36.3; H, 2,42, 2.33; -OMe, 12.1, 12.4%; Calc. for C H, FO Si C, 35.9; H, 2.6; OMe, 12.6%.

EXAMPLE 4 222 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 614 partsof compound A, 0.5 part of bis(diethylsulphide) platinum(II) chlorideand 210 parts of toluene were heated under reflux for 30 minutes.Infra-red analysis of the mixture showed that no Si-H containingmaterial was present. Removal of volatile materials left a residue of800 parts of the compound (Me SiO) Si(- Me)CI-I CH CH oC l-I OC, F,corresponding to 96 percent of theory. An analytical sample was obtainedby distillation in vacuo. b.p. 142/0.4 mm. (Found: C, 37.3, 37.0; H,3.69, 3.68 percent. C H F O Si requires C, 37.3; H, 3.74 percent).

EXAMPLE 5 720 parts of the product of Example 2 were dissolved in 2,500parts of acetone and 500 parts of water added. When the exothermicreaction had subsided the mixture was heated under reflux for 30minutes, after which all volatiles were distilled off to a finalpressure of 0.5 mm. Hg at 100C. The product wasa clear viscous liquid at100C, becoming a highly viscous fluid at 205C. It was a polysiloxanecontaining the repeating Unlt.

Si-O 2):

O mFIn (Found: C, 35.7, 35.3; H, 1.50, 1.80; Si, 4.18, 4.45 percent; c,,H,,F,,o,si requires C, 35.6; H, 1.9; Si, 4.2%.

EXAMPLES 6-10 Five substituted polysiloxanes having the formula r rM8aSiO O mFm wherein n was 8, 25, 50, 98 and 200 were prepared asfollows;

Thepolysiloxane Me SiO(SiMel-IO),.SiMe 1.7 parts of bis(diethylsulphide) platinum(ll)chloride, 500 parts of compound A and1,000 parts of toluene were heated to reflux. A lower layer separatedout a few minutes after reflux was established. The mixtures were heatedunder reflux for 4 hours, then solvent was removed on a rotaryevaporator. Theoretical yields were obtained. Parts of startingpolysiloxane used are given in Table I.

TABLE I Example n Parts of Polysiloxane A foaming solution was preparedcomprising a 2 percent solution in perchloroethylene of a mixture ofbutyl titanate (3 parts), a methylpolysiloxane copolymer containing MesiO and SiO units in the ratio 1.2:1 (3 parts), a dimethylpolysiloxanehaving a viscosity of 300 cS at 25C (3 parts) and a dimethylpolysiloxanehaving a viscosity of 30,000 cS at 25C (1 part). The siloxane ofexamples 6-10, and a cyclic siloxane F l 1 SiO where tested fordefoaming activity towards this solution. An aliquot of the foamingsolution was treated with 50 ppm. of the siloxane as a 1 percentsolution in CFCl The solution was'shaken for 30 seconds and the timeneeded for the foam to break was noted and is given in Table II.

TABLE II Siloxane Defoam time (sec.)

6 l2.8 7 I25 8 l7.6 9 l7.l 10 21.4 F 12.1

In the absence of antifoam the foam was stable for 5 minutes.

EXAMPLE 1 1 Preparation of CwFWO S OzNIICIIzCIIgCHz S i(() 0211.5)1!

Reagents Q 20Jg. (0.4m).

OmFmO S0901 obtained by a method described in UK Patent application No.8295/71 (7 amino propyl triethoxy silane) 82.8g (0.4m) Sodium carbonate43g (0.4m) Arcton" [l3 l.2 litres (l,l,2-trifluoro-l .2,2-

trichloroethane) in complete Spectroscopic Measurements Mass No parention observed Ions produced at mle 814 corresponding to parent C,H-,

do. 842 do. do. CH,

d0. 220 (I0, NH(CHg)3Si( 2 s): do. I74 do. loss of C l'hOH from ion do.l63 do. Si(OC H NMR F peaks at following positions in ppm Solvent CCl,

F30 F: 55.3) oFFo-o=c o- (78. 8? C .532 (41. 5;?

The same compound was also prepared by the following sequence ofreactions:

bis(diethyl sulphide) platinum II chloride (Et 0 )a s iH Si-(O-CHg-CHa);

EXAMPLE l2 Reagents 010F100SOzNH(CHz)aSi(OEl;)a

Potassium hydroxide lsopropanol A solution of the fluorosilane (preparedas described in Example 1 l) in isopropanol containing finelygroundpotassium hydroxide was stirred at 25C for hours. The solvent was thenremoved in vacuo and the polysiloxane dissolved in 1,1,2-trifluoro-1,2,2- trichloroethane. The resultant solution was washedwith water, dried and concentrated to afford a percent w/w solutionwhich was useful for coating glass surfaces.

EXAMPLE 13 Chemical'lndustries Limited). The 1.2 kg mixture was chargedto a 30 litre vessel with 20 litres of water at less than 25C. A stirrerin the vessel ran at 450 rpm while the temperature was raised to C, andmaintained at this temperature for 2 hours. The temperature was allowedto fall to less than 30C, the stirrer stopped, and

theslurry from the vessel discharged to a dewatering table with 400 umopenings. The product retained on the table was dried for 2 hours at200C, and baked for 3 hours at 280C. The cool product was seievedthrough a sieve having 1,000 um openings. The product passing throughthe sieve was in the form of smooth glass filled PTFE agglomerates witha measured glass content of 24.9 percent. Thus of the 27 percent of theglass originally present, only slightly in excess of 2 percent hadfailed to be agglomerated with the PFTE and the process was thereforeconsidered successful.

EXAMPLE 14 Example 13 was repeated except that the solution mixed withthe 400 g of glass fibre consisted of 18 mls of a 1 percent solution ofthe compound prepared as described in Example 3 to which had been added31 mls of a 1 percent aqueous solution of acetic acid. The productpassing through the sieve having 1,000 um openings was an agglomeratedglass filled PTFE with a measured glass content of 24.8 percent. Theagglomerates had smooth surfaces. The process was therefore ratedsuccessful.

What we claim is:

1. An organosilicon compound of the general formula:

where R is a divalent group selected from the group consisting ofoxygen, alkylene groups having not more than 8 carbon atoms,polyoxyalkylene diol residues, phenyleneoxy groups and phenyleneoxygroups containing substituents selected from the group consisting oflower alkyl and alkoxy groups and halogen atoms and in the case where Ris a phenyleneoxy or a substituted phenyleneoxy group, the group R beingoptionally linked to the group C,, H via a group selected from the groupconsisting of sulphonamido and carboxyl groups, R is selected from thegroup consisting of methyl and phenyl groups, X is selected from thegroup consisting of halogen atoms, lower alkoxy groups, substitutedlower alkoxy groups and polyoxyalkylene groups, Z is selected from thegroup consisting of lower alkyl groups and phenol, a is 0 or I, b is 0,l or 2, c is O, 1, 2, or 3, 12 +0 is not greater than 3, dis 0,1, 2, or3, e is 0 or 1 and d+e is not greater than 3, n is 8, 10, or 12, m is 2,3 or 4, x is a positive integer, when b +c is 3, v is 0, and when b +cis not greater than 2, y is a positive integer.

2. Organosilicon compounds as claimed in claim I wherein the group X isselected from the group consisting of chlorine, methoxy and ethoxygroups.

3. organosilicon compounds as claimed in claim 1 wherein Z is a methylgroup. p

4. A process for the production of organosilicon compounds as claimed inclaim 1 wherein a is l and R is selected from the group consisting ofphenyleneoxy and substituted phenyleneoxy groups comprising reacting atetrafluoroethylcne oligomer of the general formula C F where n is 8,10, or 12 with a phenol selected from the group consisting ofallylphenol and substituted allylphenols and thereafter reacting theproduct so obtained with an organosilicon compound containing at leastone silicon-bonded hydrogen atom selected from the group consisting ofsilanes and siloxanes.

5. A process for the production of organosilicon compounds as claimed inclaim 1 comprising reacting a compound of the general formula C F OC HSO Cl where n is 8, 10 or 12 with a y -aminoalkyl silicon compoundselected from the group consisting of silanes and siloxanes.

6. A process according to claim 5 wherein the -y aminoalkyl group is a yaminopropyl group.

7. A process for the production of organosilicon compounds as claimed inclaim 1 comprising reacting a compound of the general formula C,,F ,,OCH SO Cl where n is 8, 10 or 12 with an olefin selected from the groupconsisting of allylamine and alkylallylamines and thereafter reactingthe product with a silicon compound containing at least onesilicon-bonded hydrogen atom selected from the group consisting ofsilanes and siloxanes.

8. A process for the production of an organosilicon compound as claimedin claim 1 comprising reacting a compound of the general formula C,,Fwhere n is 8, 10 or 12 with an alkenyl magnesium bromide and thereafterreacting the product with a silicon compound containing at least onesilicon-bonded hydrogen atom selected from the group consisting ofsilanes and

1. AN ORGANOSILICON COMPOUND OF THE GENERAL FORMULA: (CNF2N-1 RNCMH2MSIRB1 XCO(3-B-C)/2)X (ZDHE SIO(4-D-E)/2)Y WHERE R IS A DIVALENT GROUPSELECTED FROM THE GROUP CONSISTING OF OXYGEN, ALKYLENE GROUPS HAVING NOTMORE THAN 8 CARBON ATOMS, POLYOXYALKYLENE DIOL RESIDUES, PHENYLENEOXYGROUPS AND PHENYLENEOXY GROUPS CONTAINING SUBSTITUENTS SELECTED FROM THEGROUP CONSISITING OF LOWER ALKYL AND ALKOXY GROUPS AND HALOGEN ATOMS ANDIN THE CASE WHERE R IS A PHENYLENEOXY OR A SUBSTITUTED PHENYLENEOXYGROUP, THE GROUP R BEING OPTIONALLY LINKED TO THE GROUP CM H2M VIA AGROUP SELECTED FROM THE GROUP CONSISTING OF SULPHONAMIDO AND CARBOXYLGROUPS, R1 IS SELECTED FROM THE GROUP CONSISTING OF METHYL AND PHENYLGROUPS, X IS SELECTED FROM THE GROUP CONSISTING OF HALOGEN ATOMS, LOWERALKOXY GROUPS, SUBSITUTED LOWER ALKOXY GROUPS AND POLYOXYALKYLENEGROUPS, Z IS SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL GROUPSAND PHENOL, A IS 0 OR 1, B IS 0, 1 OR 2, C IS 0, 1,2 OR 3, B+C IS NOTGREATER THAN 3, D IS 0, 1, 2, OR 3, E IS 0 OR 1 AND D+E IS NOT GREATERTHAN 3, N IS 8, 10, OR 12, M IS 2, 3 OR 4, X IS A POSITIVE INTEGER, WHENB + C IS 3 V IS 0, AND WHEN B + C IS NOT GREATER THAN 2, Y IS A POSITIVEINTEGER.
 2. Organosilicon compounds as claimed in claim 1 wherein thegroup X is selected from the group consisting of chlorine, methoxy andethoxy groups.
 3. Organosilicon compounds as claimed in claim 1 whereinZ is a methyl group.
 4. A process for the production of organosiliconcompounds as claimed in claim 1 wherein a is 1 and R is selected fromthe group consisting of phenyleneoxy and substituted phenyleneoxy groupscomprising reacting a tetrafluoroethylene oligomer of the generalformula CnF2n where n is 8, 10, or 12 with a phenol selected from thegroup consisting of allylphenol and substituted allylphenols andthereafter reacting the product so obtained with an organosiliconcompound containing at least one silicon-bonded hydrogen atom selectedfrom the group consisting of silanes and siloxanes.
 5. A process for theproduction of organosilicon compounds as claimed in claim 1 comprisingreacting a compound of the general formula CnF2nOC6H4SO2Cl where n is 8,10 or 12 with a gamma -aminoalkyl silicon compound selected from thegroup consisting of silanes and siloxanes.
 6. A process according toclaim 5 wherein the gamma aminoalkyl group is a gamma aminopropyl group.7. A process for the production of organosilicon compounds as claimed inclaim 1 comprising reacting a compound of the general formulaCnF2nOC6H4SO2Cl where n is 8, 10 or 12 with an olefin selected from thegroup consisting of allylamine and alkylallylamines and thereafterreacting the product with a silicon compound containing at least onesilicon-bonded hydrogen atom selected from the group consisting ofsilanes and siloxanes.
 8. A process for the production of anorganosilicon compound as claimed in claim 1 comprising reacting acompound of the general formula CnF2n where n is 8, 10 or 12 with analkenyl magnesium bromide and thereafter reacting the product with asilicon compound containing at least one silicon-bonded hydrogen atomselected from the group consisting of silanes and siloxanes.